U.S. patent application number 12/091083 was filed with the patent office on 2008-10-16 for polyester-polysiloxane copolymers and process for their preparation.
This patent application is currently assigned to WACKER CHEMIE AG. Invention is credited to Sandra Bachmaier, Oliver Schaefer.
Application Number | 20080255317 12/091083 |
Document ID | / |
Family ID | 37685222 |
Filed Date | 2008-10-16 |
United States Patent
Application |
20080255317 |
Kind Code |
A1 |
Schaefer; Oliver ; et
al. |
October 16, 2008 |
Polyester-Polysiloxane Copolymers and Process for their
Preparation
Abstract
Polyester/polysiloxane copolymers are prepared by ring-opening
synthesis of hydroxyalkyl- or aminoalkyl functional
organopolysiloxanes from a cyclic silazane and an Si--OH functional
polysiloxane, followed by reaction with a cyclic lactone such as a
caprolactone. The process tolerates functional groups on the
polysiloxane segments which are not possible in other synthetic
methods.
Inventors: |
Schaefer; Oliver;
(Burghausen, DE) ; Bachmaier; Sandra; (Eggelsberg,
AT) |
Correspondence
Address: |
BROOKS KUSHMAN P.C.
1000 TOWN CENTER, TWENTY-SECOND FLOOR
SOUTHFIELD
MI
48075
US
|
Assignee: |
WACKER CHEMIE AG
Munich
DE
|
Family ID: |
37685222 |
Appl. No.: |
12/091083 |
Filed: |
October 13, 2006 |
PCT Filed: |
October 13, 2006 |
PCT NO: |
PCT/EP2006/067397 |
371 Date: |
April 22, 2008 |
Current U.S.
Class: |
525/415 |
Current CPC
Class: |
C08G 77/445
20130101 |
Class at
Publication: |
525/415 |
International
Class: |
C08G 63/91 20060101
C08G063/91 |
Foreign Application Data
Date |
Code |
Application Number |
Oct 27, 2005 |
DE |
10 2005 051 579.7 |
Claims
1.-10. (canceled)
11. A process for preparing polyester-polysiloxane block copolymers
of the formula (I), (A).sub.aB (I) in which a is an integer >1,
A denotes a polyester unit of the formula (II)
H--[O--(CR.sup.1.sub.2).sub.n--CO--].sub.m--X--R.sup.2-- (II), in
which X is oxygen or NR.sup.x, R.sup.1 are identical or different,
monovalent, substituted or unsubstituted hydrocarbon radicals or
hydrogen, R.sup.2 are divalent, substituted or unsubstituted
organic hydrocarbon radicals having 1 to 40 carbon atoms,
individual, adjacent carbon atoms optionally replaced by oxygen
atoms, R.sup.x are monovalent, substituted or unsubstituted
hydrocarbon radicals having 1 to 20 carbon atoms, individual,
adjacent carbon atoms optionally replaced by oxygen atoms, and/or
are hydrogen or SiR'.sub.2--R.sup.2--NR.sup.x, in which R' are
identical or different, monovalent, substituted or unsubstituted
hydrocarbon radicals, n is an integer from 3 to 10 and m is an
integer from 1 to 1000, and B is a polysiloxane unit of the formula
(III)
(R.sup.3.sub.2SiO.sub.2/2).sub.p(R.sup.3.sub.3SiO.sub.1/2).sub.q[O.sub.1/-
2H].sub.r[O.sub.1/2SiR.sup.4.sub.2].sub.t (III) in which R.sup.3
are identical or different, substituted or unsubstituted,
aliphatically saturated or unsaturated, linear, cyclic or branched
hydrocarbon or hydrocarbonoxy radicals having 1 to 20 carbon atoms,
or substituted or unsubstituted aromatic hydrocarbon or
hydrocarbonoxy radicals having 6 to 20 carbon atoms, R.sup.4 are
identical or different, substituted or unsubstituted, aliphatically
saturated, linear, cyclic or branched hydrocarbon or hydrocarbonoxy
radicals having 1 to 20 carbon atoms, or substituted or
unsubstituted aromatic hydrocarbon or hydrocarbonoxy radicals
having 6 to 20 carbon atoms, P is an integer from 0 to 3000, q is
an integer from 0 to 50, r is an integer .gtoreq.0, and t is an
integer .gtoreq.1, comprising reacting cyclic esters of the formula
(IV) ##STR00005## in which R.sup.1 is as defined above and b
denotes an integer from 3 to 10, with siloxanes of the formula (V)
(R.sup.3.sub.2SiO.sub.2/2).sub.p(R.sup.3.sub.3SiO.sub.1/2).sub.q[O.sub.1/-
2H].sub.r[O.sub.1/2SiR.sup.4.sub.2--R.sup.2--X--H].sub.t (V) in
which X, R.sup.2, R.sup.3, R.sup.4, p, q, r, and t are as defined
above, with the proviso that the siloxane of the formula (V) is
prepared by reacting a compound of the general formula (VI)
(R.sup.3.sub.2SiO.sub.2/2).sub.p(R.sup.3.sub.3SiO.sub.1/2).sub.q[O.sub.1/-
2H].sub.s (VI), with a cyclic compound of the formula (VII)
##STR00006## or, or polymerization product thereof, in which X,
R.sup.2, R.sup.3, R.sup.4, p, and q are as defined above and s is
an integer .gtoreq.1.
12. The process of claim 11, wherein a has the value 1 or 2.
13. The process of claim 11, wherein the sum of (p+q+s+t) is a
number from 5 to 1000.
14. The process of claim 11, wherein as a cyclic compound of the
formula (VII), a compound of the formula (VIII) ##STR00007## or
polymerization product thereof is used, in which R.sup.2 is a
divalent propyl or butyl radical and R.sup.4 is a methyl radical,
wherein in the radicals R.sup.2 and R.sup.4 it is possible for a
methylene group to be replaced by an oxygen atom.
15. The process of claim 11, wherein as a cyclic compound of the
formula (VII) a compound of the general formula (IX) ##STR00008##
is used, in which R.sup.2 is a divalent propylene radical, R.sup.4
is a methyl radical, and R.sup.x is hydrogen or a
--Si(Me).sub.2-C.sub.3H.sub.6--NH.sub.2 radical.
16. The process of claim 11, wherein in the process step for the
preparation of the compound of the formula (V) a catalyst selected
from the group consisting of organic or inorganic Lewis acid or
Lewis base, organic Bronstedt acid or base, organometallic
compounds or halide salts, is used as a catalyst.
17. The process of claim 11, wherein in the process step for the
preparation of the compound of the formula (I) an organotin
compound is used as catalyst.
18. The process of claim 11, wherein at least one radical R.sup.3
or R.sup.4 in the formula (III) is an unsaturated alkyl radical
having 1 to 6 carbon atoms.
19. The process of claim 18, wherein at least one radical R.sup.3
or R.sup.4 in the formula (III) is a vinyl or allyl radical.
20. A polyester-polysiloxane block copolymer prepared by the
process of claim 18.
21. A polyester-polysiloxane block copolymer prepared by the
process of claim 19.
Description
[0001] The invention relates to a process for preparing
polyester-polysiloxane copolymers.
[0002] Polyester-polysiloxane copolymers are known, for example,
from patent specifications U.S. Pat. No. 4,663,413, U.S. Pat. No.
4,963,595, and U.S. Pat. No. 5,235,003. Specific embodiments of
this class of product are likewise described by Muelhaupt et al. in
Angew. Makromol. Chem. 223 (1994) 47-60, Polym. Mater. Sci. Eng. 70
(1993) 4, and J. Appl. Polym. Sci. 54 (6) (1994) 815-26.
[0003] The preparation of these products in accordance with the
prior art is accomplished by ring-opening polymerization of cyclic
esters, such as .epsilon.-caprolactone, for example, under the
action of catalysts, such as tin salts, for example. Starting
products for this preparation are hydroxyalkylsiloxanes or else
aminoalkylsiloxanes.
[0004] The corresponding hydroxyalkylsiloxanes, for example, can be
obtained by equilibration reactions of functional dimers with
cyclic siloxanes, or hydrosilylation reactions of Si--H-functional
siloxanes of desired architecture and chain length with
alkenyl-functional alcohols or amines. In this case the quality of
the end product in terms of degree of functionalization, chemical
purity, and impurities is heavily dependent on the reaction pathway
used.
[0005] The equilibration reactions of functional dimers with cyclic
siloxanes is feasible only for the amino-functional siloxane
reactants. Hydroxy-functional siloxanes, in contrast, cannot be
prepared in sufficient purity by way of equilibration reactions,
since the equilibration reaction is accompanied by transformation
of carbinol groups into Si--O--C groups, with loss of the carbinol
function. Siloxanes prepared by this equilibration pathway,
furthermore, permit only limited product architectures. Here,
therefore, the preparation of siloxane-polyester copolymers with an
A-B block structure is not possible.
[0006] The hydrosilylation of Si--H-functional siloxanes with
alkenyl-functional alcohols or amines, which is used for presently
commercially available products, has the disadvantage that the
hydrosilylation reaction may be accompanied by secondary reactions
involving hydrogen elimination, these reactions leading, with the
formation of Si--N--C or Si--O--C groups, to unreactive alkenyl end
groups, which are no longer able to initiate ring-opening
polymerization of cyclic esters and which therefore lead to a
reduction in product quality. A further disadvantage here is that
functional groups in the siloxane chain, such as vinyl groups, for
example, are not tolerated in this process pathway and, for
example, are consumed by reaction with crosslinking.
[0007] A further disadvantage of the existing techniques for the
preparation of the amino-functional or carbinol-functional
siloxanes as starting material for preparing the
polycaprolactone-siloxane-polycaprolactones lies in the general use
of Si--H functional compounds, which on the one hand do not allow
simultaneous use of vinyl-substituted siloxanes but on the other
hand, owing to the high price of corresponding Si--H functional
silanes or siloxanes as starting compounds, have a distinctly
deleterious effect on the preparation costs of the
polycaprolactone-siloxane-polycaprolactone end product.
[0008] It was an object of the present invention, in the light of
the above-described prior art, to provide a process for the
preparation of polyester-polysiloxane copolymers that on the one
hand is variable in terms of desired polymer structures, such as,
A-B or A-B-A block copolymers, for example, and at the same time,
where appropriate, is tolerant of the introduction of functional
groups, such as alkenyl groups, for example, in the siloxane main
chain, and which additionally has economic advantages, yet allows a
very high level of chemical purity on the part of the desired
products.
[0009] Surprisingly it has now been found that the use of
aminoalkyl-functional or hydroxyalkyl-functional siloxanes which
have been prepared by reacting functional siloxanes or silazanes
with Si--OH functional siloxanes meets all of the requirements of a
flexible operation which can lead both to A-B-A and to A-B
structures and which is also, moreover, tolerant of functional
groups in the siloxane chain. The use of the Si--OH functional
siloxanes as a siloxane component, which are significantly easier
and more cost-effective to prepare, significantly minimizes the
preparation expenditures for the
polycaprolactone-siloxane-poly-caprolactone end products.
[0010] This process for the functionalization of silicones with
organofunctional groups has the advantage, furthermore, that it
leads not only to aminoalkyl-functional siloxanes, as described,
for example, in DE 100 51 886 C1 and DE 103 03 693 A1, but also to
hydroxyalkyl-functional compounds, as described, for example, in DE
101 09 842 A1. It is possible here to prepare not only
monofunctional siloxanes but also difunctional siloxanes or
polyfunctional silicone resins or silicas.
[0011] The starting compounds are Si--OH-functional siloxanes,
which can be converted easily and in high purity into the desired
organofunctional siloxanes. Functional groups, such as vinyl
groups, for example, in the siloxane chain are easily obtainable
both in the case of hydroxyalkyl-functional siloxanes and in the
case of aminoalkyl-functional siloxanes.
[0012] At the same time the Si--OH-functional siloxanes used as a
reactant are available in large quantities at relatively favorable
prices and in a high degree of variability, with the consequence
that the siloxanes thus prepared are an ideal building block for
the preparation of siloxane-polyester copolymers.
[0013] The invention accordingly provides a process for preparing
polyester-polysiloxane block copolymers of the general formula
(I),
(A).sub.aB (I)
[0014] in which
[0015] a is an integer .gtoreq.1, [0016] A denotes a polyester unit
of the general formula (II)
[0016] H--[O--(CR.sup.1.sub.2).sub.n--CO--].sub.m--X--R.sup.2--
(II), [0017] in which [0018] a denotes oxygen or NR.sup.x, [0019]
R.sup.1 denotes identical or different, monovalent, substituted or
unsubstituted hydrocarbon radicals or hydrogen, [0020] R.sup.2
denotes divalent, substituted or unsubstituted organic hydrocarbon
radicals having 1 to 40 carbon atoms, it being possible for
individual carbon atoms to be replaced by oxygen atoms, [0021]
R.sup.x denotes monovalent, substituted or unsubstituted
hydrocarbon radicals having 1 to 20 carbon atoms, it being possible
for individual carbon atoms to be replaced by oxygen atoms, or
denotes hydrogen or --SiR'.sub.2--R.sup.2--NR.sup.x, in which R'
denotes identical or different, monovalent, substituted or
unsubstituted hydrocarbon radicals, [0022] n denotes an integer
from 3 to 10 and [0023] m denotes an integer from 1 to 1000, and
[0024] B denotes a polysiloxane unit of the general formula
(III)
[0024]
(R.sup.3.sub.2SiO.sub.2/2).sub.p(R.sup.3.sub.3SiO.sub.1/2).sub.q[-
O.sub.1/2H].sub.r[O.sub.1/2SiR.sup.4.sub.2].sub.t (III) [0025] in
which [0026] R.sup.3 denotes identical or different, substituted or
unsubstituted, aliphatically saturated or unsaturated, linear,
cyclic or branched hydrocarbon or hydrocarbon-oxy radicals having 1
to 20 carbon atoms, or substituted or unsubstituted aromatic
hydrocarbon or hydrocarbon-oxy radicals having 6 to 20 carbon
atoms, [0027] R.sup.4 denotes identical or different, substituted
or unsubstituted, aliphatically saturated, linear, cyclic or
branched hydrocarbon or hydrocarbon-oxy radicals having 1 to 20
carbon atoms, or substituted or unsubstituted aromatic hydrocarbon
or hydrocarbon-oxy radicals having 6 to 20 carbon atoms, [0028] p
is an integer from 0 to 3000, [0029] q is an integer from 0 to 50,
[0030] r is an integer.gtoreq.0, and [0031] t is an
integer.ltoreq.1, [0032] which through the reaction of cyclic
esters of the general formula (IV)
[0032] ##STR00001## [0033] in which R.sup.1 is as defined above and
[0034] b denotes an integer from 3 to 10, [0035] with siloxanes of
the general formula (V)
[0035]
(R.sup.3.sub.2SiO.sub.2/2).sub.p(R.sup.3.sub.3SiO.sub.1/2).sub.q[-
O.sub.1/2H].sub.r[O.sub.1/2SiR.sup.4.sub.2--R.sup.2--X--H].sub.t
(V) [0036] in which X, R.sup.2, R.sup.3, R.sup.4, p, q, r, and t
are as defined above,
[0037] characterized in that the compound of the general formula
(V) is prepared through reaction of the compound of the general
formula (VI)
(R.sup.3.sub.2SiO.sub.2/2).sub.p(R.sup.3.sub.3SiO.sub.1/2).sub.q[O.sub.1-
/2H].sub.s (VI)
[0038] with a cyclic compound of the general formula (VII)
##STR00002##
[0039] or polymerization products thereof, in which X, R.sup.2,
R.sup.3, R.sup.4, p, and q are as defined above and s is an integer
.gtoreq.1.
[0040] If compounds of the general formula (VII) are used, they
react easily and selectively, with good yields, with silanol end
groups.
[0041] Compounds of the general formula (VII) are stable, are
storable, can be synthesized very easily from simple precursors, in
accordance, for example, with German laid-open specification DE 15
93 867 A1, and are therefore especially suitable for use on the
industrial scale.
[0042] The C.sub.1-C.sub.20 hydrocarbon radicals and
C.sub.1-C.sub.20 hydrocarbonoxy radicals R.sup.3 and R.sup.4 may be
aliphatically saturated or unsaturated, aromatic, straight-chain or
branched. R.sup.3 and R.sup.4 preferably have 1 to 12 atoms, more
particularly 1 to 6 atoms, preferably only carbon atoms, or an
alkoxy oxygen atom and otherwise only carbon atoms.
[0043] Preferably R.sup.3 and R.sup.4 are straight-chain or
branched C.sub.1-C.sub.6 alkyl radicals or phenyl radicals. The
radicals methyl, ethyl, phenyl, vinyl, and trifluoropropyl are
particularly preferred. Preference is given to preparing the
compounds of the general formula (V) in which R.sup.3 denotes a
methyl radical or vinyl radical and R.sup.4 denotes a methyl
radical.
[0044] In one preferred embodiment at least one radical R.sup.3 or
R.sup.4 in the general formula is an unsaturated alkyl radical
having 1 to 6 carbon atoms and with particular preference a vinyl
or allyl radical. Hence, for the first time, access is made
possible to polyester-polysiloxane block copolymers of the general
formula (I) that have unsaturated and hence reactive alkyl radicals
in the silicone components. These polyester-polysiloxane block
copolymers are likewise provided by this invention and make it
possible, for example, for the polyester-polysiloxane block
copolymers to be additionally crosslinked in a matrix or on a
surface.
[0045] Preferably a is selected from the group containing 1 and 2.
The inventively prepared compounds of the general formula (I) may
be linear or branched.
[0046] The values of n are preferably not more than 6 and with
particular preference 4 or 5.
[0047] Index m preferably has values of not more than 200 and with
particular preference values of 1 to 100.
[0048] The sum of (p +q +s +t) is preferably a number from 3 to 20
000 and more particularly a number from 5 to 1000.
[0049] One preferred embodiment of an organosiloxane of the general
formula (III) is a linear silicone polymer with p greater than or
equal to 1, q and r equal to 0, and t equal to 2. A
further-preferred embodiment for an organosiloxane of the general
formula (III) is a linear silicone polymer with p greater than or
equal to 1, q equal to 1, r equal to 0, and t equal to 1. The
preferred organosiloxanes of the general formula (III) may be
distributed either monomodally or multimodally; at the same time
they may be present in a narrow or very broad distribution.
[0050] The cyclic compound of the general formula (VII) is
preferably a five- to seven-membered ring which in addition to its
effective synthetic access at the same time also has good
reactivity toward silanol groups.
[0051] As compounds of the general formula (VII) it is preferred to
use compounds of the general formula (VIII)
##STR00003##
[0052] in which
[0053] R.sup.2 and R.sup.4, and have the above definitions.
Preferably here R.sup.4 is a methyl radical and R.sup.2 is a
divalent propyl or butyl radical, in which a methylene group may be
replaced by an oxygen atom. With very particular preference R.sup.2
is a divalent propyl radical or a divalent
--CH.sub.2--CH.sub.2--O--CH.sub.2-- radical.
[0054] Also preferred as compounds of the general formula (VII) are
compounds of the general formula (IX)
##STR00004##
[0055] in which
[0056] R.sup.x and R.sup.4 have the definitions above and R.sup.2
preferably represents a divalent propylene or butylene radical.
With particular preference R.sup.2 denotes a divalent propylene
radical, R.sup.4 denotes a methyl radical, and R.sup.x denotes
hydrogen or an --Si(Me).sub.2--C.sub.3H.sub.6--NH.sub.2
radical.
[0057] The process for the preparation of the compounds of the
formula (V) can be carried out without catalysis preferably at
temperatures of 0.degree. C. to 200.degree. C. It is preferred,
however, to use reaction temperatures of at least 20.degree. C. The
process, however, can be further improved by adding certain
catalysts. These catalysts are acidic or basic compounds and make
it possible for both reaction times and reaction temperatures to be
reduced.
[0058] The catalyst used in this case is an organic or inorganic
Lewis acid or Lewis base, such as, for example, organic Bronstedt
acid or base, an organometallic compound or a halide salt.
Preferred acids used are carboxylic acids, partially esterified
carboxylic acids, more particularly monocarboxylic acids,
preferably formic acid or acetic acid, or unesterified or partially
esterified mono-, oligo- or polyphosphoric acids. Preferred bases
employed are preferably alkylammonium hydroxides, alkylammonium
silanolates, ammonium alkoxides, alkylammonium fluorides, amine
bases or metal alcoholates or metal alkyls. Preferred metal
alcoholates are lithium or sodium alcoholates. Preferred
organometallic reagents are organotin compounds, organozinc
compounds or alkoxytitanium compounds, or organolithium compounds
or grignard reagents. Preferred salts are tetraalkylammonium
fluorides.
[0059] After the functionalization reaction of the silanol groups,
the catalysts used are deactivated preferably by addition of what
are called anticatalysts or catalyst poisons, before they can lead
to cleavage of the Si--O--Si groups. This secondary reaction is
dependent on the catalyst used and need not necessarily occur, so
that it may also be possible to forgo deactivation. Examples of
catalyst poisons are acids, for example, when using bases, and
bases, for example, when using acid, which leads in its end effect
to a simple neutralization reaction with corresponding
neutralization products, which where appropriate can be filtered
off or extracted. Depending on the use of the product, the
corresponding reaction product of catalyst with catalyst poison can
either be removed from the product or remain in the product.
[0060] In the process for the preparation of compounds of the
general formula (V) the amount of the compound used with units of
the general formula (VII) is dependent on the number r of the
silanol groups to be functionalized in the organosiloxane of the
general formula (VI). If the desire, however, is to achieve
complete functionalization of the OH groups, then the compound with
units of the general formula (VII) must be added in at least
equimolar amounts. If a compound with units of the general formula
(VII) is used in excess, then unreacted compound can subsequently
either be distilled off or hydrolyzed and, if desired, likewise
distilled off.
[0061] This process may be carried out either with solvents
included or without the use of solvents, in suitable reactors. It
is operated, where appropriate, under reduced pressure or under
superatmospheric pressure, or at standard pressure (0.1 MPa).
[0062] If solvents are used, preference is given to inert, more
particularly aprotic solvents such as aliphatic hydrocarbons,
examples being heptane or decane, and aromatic hydrocarbons,
examples being toluene or xylene. It is likewise possible to use
ethers, such as THF, diethyl ether or MTBE, for example. The amount
of solvent should be sufficient to ensure adequate homogenization
of the reaction mixture. Solvents or solvent mixtures with a
boiling point or boiling range of up to 120.degree. C. at 0.1 MPa
are preferred.
[0063] The process step for the preparation of the compounds of the
formula (I) can be carried out at temperatures of 20.degree. C. to
250.degree. C. Preferably, however, reaction temperatures of at
least 50.degree. C. are used. With particular preference first of
all some of the cyclic ester is caused to be consumed by reaction
at relatively low temperatures of 50.degree. C. to 100.degree. C.,
so that the organofunctional group on the siloxane of the general
formula (V) can be stabilized against thermal degradation by means
of the esterification that takes place. After that the temperature
is raised, in order to increase the reaction rate, to 100.degree.
C. to 200.degree. C. The reaction time is heavily dependent on the
catalysts used. Commonly used here are the catalysts that are used
in the literature for the synthesis of caprolactone copolymers.
These are, especially, organotin compounds, but also alkoxytitanium
compounds. Their amount, based on the total amount of the silicone
copolymer, is about 20-2000 ppm. Preferably, however, 100-1000 ppm.
The reaction time is approximately 0.5 to 48 hours, but preferably
2-10 hours. Subsequently, excess caprolactone or siloxane
impurities are separated off by distillation under reduced pressure
and at elevated temperature. Preference is given in this case to
pressures of below 100 mbar and temperatures of more than
100.degree. C. This process can be carried out either with
inclusion of solvents or else without the use of solvents, in
suitable reactors. In that case it is operated, where appropriate,
under reduced pressure or under superatmospheric pressure, or at
standard pressure (0.1 MPa). The process can be carried out
continuously or discontinuously.
[0064] If solvents are used, preference is given to inert, more
particularly aprotic solvents such as aliphatic hydrocarbons,
examples being heptane or decane, and aromatic hydrocarbons,
examples being toluene or xylene. The amount of solvent should be
sufficient to ensure adequate homogenization of the reaction
mixture. Solvents or solvent mixtures with a boiling point or
boiling range of up to 120.degree. C. at 0.1 MPa are preferred.
[0065] All of the above symbols in the above formulae have their
definitions in each case independently of one another.
[0066] The block copolymers of the present invention display
different outstanding properties on adjustment of the degree of
polymerization and of the ratio of polysiloxane component to
aliphatic polyester block. The block copolymers of the invention
may find broad application as they are or as additives in various
resins. Owing to the chemical bonding of polysiloxane and aliphatic
polyesters, the block copolymers of the invention display
surprisingly improved properties in the form of simple mixtures of
the parent polymers. Furthermore, they do not show any bleeding
effects.
[0067] The polyester-polysiloxane copolymer of the invention as it
is can be used as an adhesive, as a coating, as cosmetics, as a
wax, as textile treatment agents, as an additive to plastics and
also in the case of mechanical or electrical components which are
required to have a nonabrasive or antislip effect, as protectants
with repellent effect, as treatment agents, as a thermally
conductive paste together with fillers, as a heat-regulating
coating material, as a lubricant, and as an interlayer or outer
layer for flat screens, wind-shields, window glass, and safety
glass.
[0068] The polyester-polysiloxane copolymers of the invention can
likewise be used for the majority of known uses of polysiloxanes;
on account of their high affinity for base materials, however, as a
result of the aliphatic polyester blocks, the
polyester-polysiloxane copolymers are mostly superior to the
polysiloxanes of the prior art. The superior properties of the
polyester-polysiloxane copolymers of the invention are manifested
in their solubility in different materials, in the avoidance of
bleeding during and after shaping, in the reduction of migration,
in the nonabrasive effect, in the gas permeability, in the low
bioactive effect, and also, furthermore, in their suitability as a
repellent in low-temperature applications, and in their
overcoatability.
[0069] Where the main constituent of the polyester-polysiloxane
copolymers of the invention is an aliphatic polyester block, and
where the block copolymer is used as it is, it may be used, for
example, in biodegradable resins, as an antithrombotic agent, as an
application agent in electroplating, in non-yellowing paints, as an
intermediate or surface coating for vehicles, as a binder and/or
additive for various paints and coatings, and also as a repellent.
The polyester-polysiloxane copolymer of the invention may enhance
the surface properties, such as, for example, the water repellency,
the nonabrasive effect, the antiblocking, the slip effect, the
weather resistance, the gas permeability, and the
bio-durability.
[0070] Furthermore, the polyester-polysiloxane copolymer of the
invention may, as an additive, enhance the properties of various
heat-curable resins. Examples of those resins to which the
polyester-polysiloxane copolymers can be added as additives are
epoxy resins, polyurethanes, polyureas, polyamides, brominated
epoxy resins, unsaturated polyester resins, polyester-polyether
copolymer, polyimides, melamine resins, phenolic resins, diallyl
phthalate resins, and derivatives thereof. Heat-curable resins of
this kind, modified with the polyester-polysiloxane copolymers of
the invention, have diverse possible applications: for example, as
a metal substitute in the automobile industry, as transmission
housings or as brush holders, for electrical and electronic parts,
as disconnector switches, magnetic switches, collectors, terminal
strips, connections, relays, and IFTs, electrical components, such
as plugs and ignition-coil caps for automobiles, boats or aircraft,
for example, for cladding tools, sports equipment and other
equipment, for electrical insulation, as circuit boards, as
magnetic tapes, for photographic films, paints, adhesives, and
laminating materials, and also as casting compounds. In these
utilities, various properties are improved as a result of the
addition of the polysiloxane blocks and aliphatic polyester
blocks.
[0071] Examples of the use of epoxy resins modified with
polyester-polysiloxane copolymers of the invention are electrical
and electronic components, laminated circuit boards, composite
materials, paints, adhesives, structured materials, and
anticorrosion applications. The improvement of the material
properties of epoxy resins thus modified is manifested more
significantly in comparison to the addition of conventional
polysiloxanes, owing, among other things, to their high affinity to
the epoxy resins. Through the modification of epoxy resins with the
polyester-polysiloxane copolymers of the invention it is possible
to enhance predominantly the thermal expansion coefficient, the
mechanical properties, such as modulus and flexibility, for
example, surface tack, fluidity of the composition prior to
processing and/or shaping, weather resistance, electrical
conductivity, and glass transition temperature, as a result of
which release from the mold after shaping, and shaping itself, are
significantly improved. Improvements of this kind are important for
the use of the epoxy resins in the encapsulation of LEDs, as
protective varnishes and coverings, and also as coating
material.
[0072] Examples of the use of polyurethanes modified with the
polyester-polysiloxane copolymers of the invention are
thermoplastic elastomers, urethane foams, adhesives, various paints
and coatings, urethane fibers and binders--for inks, for example.
The polyester-polysiloxane copolymers of the invention have
terminal carbinol groups which can react with isocyanates.
Accordingly they can also be used as reactants for isocyanates in
order to obtain specific properties derived from the polysiloxane
blocks and/or aliphatic polyester blocks.
[0073] The polyester-polysiloxane copolymer of the invention can be
used, furthermore, as an additive for thermoplastic resins.
Examples of such thermoplastic resins are polyacrylonitrile,
polymethacrylonitrile, polymethyl acrylate, polyacrylamide,
polymethacrylate, polymethacrylate esters, and other acrylic
resins, polystyrene, polyesters, polyamide, polyesteramide,
thermoplastic polyurethanes, polyvinyl chloride, polycarbonate,
polyacetal, polyvinylidene chloride, polyvinyl alcohol, and
cellulose derivatives. In these systems the polyester-polysiloxane
copolymer of the invention improves various properties of the
aforementioned thermoplastics, such as, for example, the slip, the
heat resistance, the impact resistance, the weather resistance, the
gas permeability, the overcoatability, the elasticity, the abrasion
resistance, and the demoldability of the resultant moldings from
the injection mold or casting mold. On account of the high
transparency of the polyester-polysiloxane copolymer of the
invention it can be used with preference as an additive for
plastics which find use in applications where there are exacting
requirements in terms of transparency, such as LEDs or screens, for
example.
[0074] As an additive in organic thermoplastics, the
siloxane-polyester copolymer may also serve as an
adhesion-promoting agent to crosslinking silicone rubbers.
[0075] In the examples which follow, all quantitative and
percentage data, unless indicated otherwise in each case, are given
by weight; all pressures are 0.10 MPa (abs.); and all temperatures
are 20.degree. C. All viscosities were determined at 25.degree.
C.
EXAMPLES
Example 1
Preparation of 2,2-dimethyl-[1,4]dioxa-2-silacyclohexane; Not
Inventive
[0076] A mixture of 103.9 g (0.75 mol) of
chloromethyl-dimethylmethoxysilane, 46.6 g (0.75 mol) of ethylene
glycol, and 200 ml of 1,4-diisopropylbenzene was heated to
150.degree. C. and stirred for 3 hours. During this time 24 g (0.75
mol) of methanol were removed by distillation. Thereafter 138.8 g
(0.75 mol) of tributylamine were added slowly dropwise at
150.degree. C. The dropwise addition was followed by a further 3
hours of stirring at 150.degree. C. The resulting salt,
tributylammonium chloride, was removed by filtration. The filtrate
was fractionally distilled twice under standard pressure, with the
fraction that goes over at 132.degree. C. affording 26 g of pure
2,2-dimethyl-2-sila-1,4-dioxane (132.23 g/mol, 20 mmol) with a
yield of 27%.
Example 2
[0077] 20 g (22.3 mmol) of a bishydroxy-terminated
poly-dimethylsiloxane having an Mn of 890 g/mol (determined by
.sup.1H-NMR spectroscopy) were reacted at 60.degree. C. with 5.9 g
of 2,2-dimethyl-[1,4]dioxa-2-silacyclohexane (44.7 mmol) and 80 mg
of lithium methanolate solution (10% strength in methanol) (300
ppm). .sup.1H-NMR and .sup.29Si-NMR showed that, after 3 hours, all
of the OH groups had been converted to hydroxyethyl methyl ether
units. This left pure bis(hydroxyethyl methyl ether)-terminated
polydimethylsiloxane.
Example 3
[0078] 1100 g of a bishydroxy-terminated polydimethylsiloxane
having an Mn of 11 000 g/mol (determined by OH number
determination) were reacted at 100.degree. C. with 26.7 g (200
mmol) of 2,2-dimethyl-[1,4]dioxa-2-silacyclohexane and 3000 mg of
lithium methanolate (10% strength in methanol) (300 ppm).
Subsequently the catalyst was neutralized by addition of weakly
acidic ion-exchange resin, which thereafter was removed by
filtration. .sup.1H-NMR and 29Si-NMR showed that, after 7 hours,
all of the OH groups had been converted to hydroxyethyl methyl
ether units. This left pure bis(hydroxyethyl methyl ether)
-terminated polydimethylsiloxane.
Example 4
[0079] 260 g of a bishydroxy-terminated polydimethylsiloxane having
an Mn of 2600 g/mol (determined by .sup.1H-NMR spectroscopy) were
reacted at 80.degree. C. with 26.7 g (200 mmol) of
2,2-dimethyl-[1,4]dioxa-2-silacyclohexane and 900 mg (300 ppm) of
lithium methanolate solution (10% strength in methanol).
.sup.1H-NMR and 29Si-NMR showed that, after 4 hours, all of the OH
groups had been converted to hydroxyethyl methyl ether units. This
left pure bis(hydroxyethyl methyl ether)-terminated
poly-dimethylsiloxane.
Example 5
[0080] 280 g of a bishydroxy-terminated polydimethylvinyl-siloxane
having a vinyl:methyl ratio of 1:4 and having an Mn of 2800 g/mol
(determined by .sup.1H-NMR spectroscopy) were reacted at 80.degree.
C. with 26.7 g (200 mmol) of
2,2-dimethyl-[1,4]dioxa-2-silacyclohexane and 900 mg (300 ppm) of
lithium methanolate solution (10% strength in methanol).
.sup.1H-NMR and 29Si-NMR showed that, after 4 hours, all of the OH
groups had been converted to hydroxyethyl methyl ether units. This
left pure bis (hydroxyethyl methyl ether)-terminated
polydimethyl-vinylsiloxane.
Example 6
[0081] 27 g of a bishydroxy-terminated
polymethyltrifluoro-propylsiloxane having a trifluoropropyl:methyl
ratio of 1:1 and having an Mn of 900 g/mol (determined by
.sup.1H-NMR spectroscopy) were reacted at 80.degree. C. with 7.9 g
(60 mmol) of 2,2-dimethyl-[1,4]dioxa-2-silacyclohexane and 90 mg
(300 ppm) of lithium methanolate solution (10% strength in
methanol). .sup.1H-NMR and 29Si-NMR showed that, after 3 hours, all
of the OH groups had been converted to hydroxyethyl methyl ether
units. This left pure bis(hydroxyethyl methyl ether)-terminated
polymethyl-trifluoropropylsiloxane.
Example 7
[0082] 33 g of a monohydroxy-terminated polydimethylsiloxane having
a molar weight of 1100 g/mol (30 mmol) (determined by .sup.1H-NMR
spectroscopy) were reacted at 80.degree. C. with 4.0 g (30 mmol) of
2,2-dimethyl-[1,4]dioxa-2-silacyclohexane and 120 mg (300 ppm) of
lithium methanolate solution (10% strength in methanol).
.sup.1H-NMR and 29Si-NMR showed that, after 3 hours, all of the OH
groups had been converted to hydroxyethyl methyl ether units. This
left pure mono(hydroxyethyl methyl ether)-terminated
polydimethylsiloxane.
Example 8
[0083] 1000 g of Me-siloxane (bishydroxy-terminated
poly-dimethylsiloxane having an average molecular weight of 3000
g/mol) were reacted at room temperature with 77.2 g of
N-((3-aminopropyl)dimethylsilyl)-2,2-di-methyl-[1-aza-2-silacyclopentane.
1H-NMR and 29Si-NMR showed that, after 2 hours, all of the OH
groups had been converted to aminopropyl units and there was no
longer any residual
N-((3-aminopropyl)dimethylsilyl)-2,2-dimethyl-1-aza-2-silacyclopentane
detectable.
Example 9
[0084] 100 g of Silicon OL [Silicone Oil] (bishydroxy-terminated
polydimethylsiloxane having an average molecular weight of 13 000
g/mol) were reacted at 50.degree. C. with 1.8 g of
N-((3-aminopropyl)dimethylsilyl)-2,2-di-methyl-[1-aza-2-silacyclopentane.
1H-NMR and 29Si-NMR showed that, after 2 hours, all of the OH
groups had been converted to aminopropyl units and there was no
longer any residual
N-((3-aminopropyl)dimethylsilyl)-2,2-dimethyl-1-aza-2-silacyclopentane
detectable.
Example 10
[0085] 100 g of Silicon OL [Silicone Oil] (bishydroxy-terminated
polydimethylsiloxane having an average molecular weight of 28 000
g/mol) were reacted at 50.degree. C. with 0.85 g of
N-((3-aminopropyl)dimethylsilyl)-2,2-di-methyl-[1-aza-2-silacyclopentane.
1H-NMR and 29Si-NMR showed that, after 2 hours, all of the OH
groups had been converted to aminopropyl units and there was no
longer any residual
N-((3-aminopropyl)dimethylsilyl)-2,2-dimethyl-1-aza-2-silacyclopentane
detectable.
Example 11-22
[0086] The respective organofunctional siloxane was mixed with
.epsilon.-caprolactone (from Solva Caprolactones). Subsequently 500
ppm of dibutyltin dilaurate were added and the reaction mixture was
heated to 70.degree. C. with stirring and held at that temperature
for 1 hour. Thereafter it was heated to 140.degree. C. and held at
that temperature for 6 hours, with stirring. Finally, under a high
vacuum (<10 mbar), about 1% to 2% of reaction mixture was
removed (siloxane rings and also .epsilon.-caprolactone). The
copolymer obtained accordingly was finally cooled and granulated.
The siloxane content was determined by means of NMR and the molar
weights by means of GPC.
TABLE-US-00001 Product Siloxane .epsilon.-Caprolactone Silicone
Amount From Amount Mn Amount content Example [g] example [g]
[g/mol] [g] [%] 11 1000 2 1000 2100 1920 52 12 1000 3 1000 20 800
1930 53 13 1000 4 1000 5680 1950 53 14 1000 5 1000 6150 1945 51 15
1000 6 1000 2280 1970 52 16 1000 7 1000 2450 1955 52 17 1000 8 1000
5710 1880 54 18 1000 4 1000 4310 1425 69 19 1000 4 1000 8450 2855
35 20 1000 5 500 4590 1475 70 21 100 9 100 24 800 180 54 22 100 10
100 49 500 180 55
* * * * *